Soap and soap products and stabilizing agent and process



HHHHHHH r- HHHHHHN Patented May 19, 1 931 HAROLD A. MORTON, OF AKRON, OHIO SOAP AND SOAP PRODUCTS AND STABILIZING AGENT AND PROCIES No Drawing.

This invention relates to the manufacture of soap and soap products, and more particularly soap or soap products made from ingredients, one or more of which ordinarily deteriorate, or develop rancidity, in a relatively short time, and the object of the present invention is to inhibit or retard this action by incorporating in the soap stock, or soap, or in one or more of the ingredients used in the manufacture thereof, a small quantity of a hydroglyoxaline derivative.

I shall hereinafter enumerate a number of the. substances which may be incorporated in, or added to, the soap or to the ingredients customarily employed in the manufacture thereof, for preventing or retarding deterioration or rancidity.

There are a great number of such hydroglyoxaline derivatives whichfunction in this These derivatives are designated in this specification by the accustomed nomenclature now in general use. The basic material, glyoxaline, from Which these substances are derived is usually given the following chemical formula:

The substances described in this specification are hydroglyoxalines or substituted hydroglyoxalines and their derivatives. In general they may be prepared by heating a 12 diamino ethane derivative with the desired aldehyde, although other methods of preparation may be employed;

Among substances which may be used in carrying my invention into effect, the following may be identified:

2-4-6 triphenyl dih droglyoxaline 24-5 trifuryl dihy roglyoxal ine 4-5 trltolyl dihydroglyoxalme dl phenyl tetra hydroglyoxaline di ortho tolyl tetra hydroglyoxalme di para tolyl tetra hydroglyoxalme di xylfil tetra hydroglyoxaline (ii a p a naphthyl tetra hydroglyoxaline di beta naphthyl tetra hydroglyoxaline phenyl ortho tolyl tetra hydroglyoxallne phenyl alpha naphthyl tetra hydroglyoxaline di phenyl 2 methyl tetra hydroglyoxaline d1 phenyl 2-viny1 tetra hydroglyoxallne ,di phenyl 2-propyl tetra hydroglyoxaline d1 phenyl -pseudo butyl tetra hydroglyoxaline di phenyl 2-propenyl tetra hydroglyoxaline di phenyl 2-furyl tetra hydroglyoxalin d1 phenyl 2-hexyl tetra hydroglyoxallne 1-3 (11 para tolyl 2-pheny1 4-5-dlmethyltetra hydroglyoxa- 3 g d1 phenyl Application filed August 1 7, 1928. Serial No. 300,372.

phenyl 3-beta naphthyl tetra hydroglyoxaline phenyl beta na ththyl Z-furyl tetra hydroglyoxaline d1 alpha napht yl 2-propy1 tetra hydroglyoxaline -3 tr1phenyl "tetra hydroglyoxaline d1 phenyl 2-methoethyl tetra hydroglyoxaline dl ortho tolyl 2propy1 tetra hydroglyoxaline.

(1 para tolyl 2-Inethyl tetra hydroglyoxaline dr xylfil 2-furyl tetra hydroglyoxaline d1 alp a naphthyl 2-propeny1 tetra hydroglyoxaline (1i alpha na hthyl 2-phenyl tetra hydroglyoxaline (11 beta nap lthyl 2-methy1 tetra hydroglyoxaline phenyl ortho tolyl 2-propyl tetra hydroglyoxaline d phenyl Jr-methyl tetra hydroglyoxaline d ortho tolyl 4-methyl tetra hydroglyoxaline d para tolyl 4-methy1 tetra hydroglyoxaline (1r xylyl 4-methyl tetra hydroglyoxaline d 1 alpha naphthyl 4-methy1 tetra hydroglyoxaline 3 beta naphthyl 4-methyl tetra hydroglyoxaline phenyl 4-ethyl tetra hydrogiyoxaline para tolyl 4-ethyl tetra hydroglyoxaline (h alpha naphthyl 2-methy1 tetra hydro'glyoxallne d1 phenyl 2-propyl ft-methyl tetra hydroglyoxaline phenyl para tolyl 2thio tetra hydroglyoxaline d1 phenyl 2-thio tetra hydroglyoxaline ortho tolyl xylyl 2-thio tetra hydroglyoxaline.

phenyl 2-thio 4-methyl tetra hydroglyoxahne phenyl 2-thio 4-5-dimethyl tetra hydroglyoxahne phenyl 2-4:dimethy1 tetra hydroglyoxaline d; phenyl 2-v1ny1 4= methyl tetra hydroglyoxaline d phenyl 2-propenyl 4-methyl tetra hydroglyoxaline dr phenyl 2-furyl 4-methyl tetra hydroglyoxaline (1 phenyl 2-hexy1 4-methyl tetra hydroglyoxaline d1 phenyl. 2-methoethyl 4-methyl tetra hydroglyoxaline -3 tr1phenyl 4-methyl tetra hydroglyoxaline d1 ortho to1y1v2-4-dimethy1-tetra hydroglyoxaline dt para tolyl 2-propyl 4-methyl tetra hydroglyoxaline d1 xylyl 2-Iuryl 4-methyl tetra hydroglyoxaline di alpha naphthyl 2-pheny1 4-metl1yl tetra hydroglyxaline dinbeta naphthyl 2-propenyl- 4-methy1 tetra hydroglye di phenyl 4-5 dimethyl tetra hydroglyoxaline di phenyl 2-meth l 4-ethy1 tetra hydroglyoxalme di ortho tolyl 2- nyl 4-ethy1 tetra hydroglyoxaline di xylyl 2-propyl 4-ethyl tetra hydroglyoxaline di1 alpha naphthyl 2-phenyl 4-ethy1 tetra hydrogly- X8. me

' phenyl 4-4-dimethyl tetra hydroglyoxaline ortho tolyl 44-dimethyl tetra hydroglyoxahne para tolyl 4-4dimethy1 tetra hydroglyoxaline xylyl 4-4-dimethyl tetra; hydroglyoxaline alpha naphthyl 4-4-dimethy1 tetra hydroglyoiraline beta naphthyl 4-4dimethyl tetra hydroglyoxallne phenyl 2-propy1 i-pseudo butyl tetra hydroglyoxaphenyl 2-4-5-trimethyl tetra hydroglyoxaline phenyl 2-pr0penyl 4'5-dimethy1 tetra hydroglyoxahenyl'2- ropyl 4-5-dimethyl tetra hydroglyoxaline phenyl 2-?ur l 4-5-dimethyl tetra hydroglyoxaline triphenyl 4-5- imethyl tetra hydroglyoxaline phenyl 2-vinyl 4-5-dimethy1 tetra hydroglyoxaline ortho tolyl 2-fury1 4-5-d1methyl tetra hydroglyoxaline line

xylyl 2-vinyl 4-5-dimethyl tetra hydroglyoxaline 1 a pha naphthyl 2-propyl 4-5-d1methy1 tetra hydrog yoxa 1 ne 1-3 di beta naphthyl 2-4-5-trimethyl tetra hydroglyoxaline 2kg phenyl 2-4-4-trimethyl tetra hydroglyoxaline 1-2-3-tr phenyl 4-4 dimethfl tetra h droglyoxa ne 3 d1 ortho tolyl 2-propy henyl 2-vinyl 4-4-d1methyl tetra ydro lyoxaline l 4-4-dimet yl tetra hydroglyoxadi phenyl 4-4-5-trimethyl tetra hydroglyoxallne 2-4-4-5-tetra methyl tetra hydroglyoxallne di phenyl 1-2-propyl 4-4-5-trimethyl tetra hydroglyoxaline 2-3 tripheny'l 4-4-5-trimethyl tetra hydroglyoxaline As indicated in the foregoing examples,

the O atom in the 2 position of substituted 2-3- di hydroglyoxaline (or of substituted 2-34-5- tetra hydroglyoxaline) may have attached thereto any of the following: H, S, CH CH CH CH CH CH ,(CH CH, CH CH CH- CH (CH CHEH CH CH CH CH CHZ, (CHQ GHEH CIL, C H 0 H,- CH C H (CH C H CH CH CH=CH, on ont, OI CH,CH CH=C(C H c H O, CH CH CH CH CH CH or in general any aliphatic or aromatic groups, whether saturated or unsaturated. These radicals I consider members of the class which may be designated, and in some appended claims are identified, by the term 2 modifying group.

Independent of the special member which may be used in 2 modifying group, one or more of the hydrogen atoms which are attached to the nitrogen atoms in the 1-3 positions may be replaced by an of the followmg: CH CH CH CH O CH (CH CH, CH OH Ol-I OH (CH3)2PCH.CH2, CHRCH CH CILCH (CHQ CHOI-LOH CHI-I59 G I- SQ C6H3(CI I3)2, C6H5CH2, (if-LOH CH CH CH, CH CH GH CH C (OJ-l C O, CH CH CH CH OH OH or in general any aliphatic or aromatic, group, whether saturated or unsaturated. These radicals I consider members of a class which may be designated, and in some of the appended claims are identified, by the term 1-3 replacement group.

One or both of the 45 positions have attached thereto oneor more of the following: H, CH OI-LCH CH H OH CH CH cn cn on cn (G CH.C CH H CH CH CH (CHQ OHCH CIL, C H C H CH C H CH) C H CH GH Cl-f= CH, CH CH,

H, H CH CH=C(C H (Ll-I O, CH OH OH CH OH CH or in general any aliphatic or aromatic groups, whether saturated or unsaturated. These I consider members of a class which may be designated, and in some of the appended claims I have identified by the term 45-modifying group.

It is to be understood, however, that stron ly negative groups such as C H OO, OH O or groups containing halogens, or nitro groups, may not be used in any position of the compound.

The above examples which are of value in practicing this invention, serve to indicate the wide range of-materials of this type which are -of value in the stabilization of soap. However, they are given only as typical examples and modifications may be made without departing from the spirit of the invention.

One of the preferred members of the above series is, 13 diphenyl 2-propyl terta hydroglyoxaline. One method of preparing this material is to heat 100 parts of 1-2 di (phenyl amino) ethane dissolved in alcohol with 40 parts of butyraldehyde under reflux for several hours. Upon cooling and crystallizing O atoms may also in the there is obtained a cream colored solid, which is dried and is then ready for use.

The tetra hydroglyoxaline derivatives referred to in this specification are prepared in by this theory but desire to claim that class of materials formed by the reaction of carbon disulphide and 12 diamino ethane derivatives.

The amount of the selected one of these substances which may be added to the ordinary soap, or soap stock, or ingredients used in the manufacture thereof, for effecting the desired result, may be varied,'but in general it will be found that good results may be obtained by adding, upon a weight basis, from 0.01% to 1.0% of the stabilizing agent to the soap or soap stock.

In utilizing my invention, the stabilizing agent may be introduced at any stage of the process of soap manufacture. For example, after the fatty acid has been obtained in the usual manner and has been saponified to produce a soap stock, I thoroughly incorporate therein 0.01% to 1.0% of 1-3 diphenyl 2-propyl tetra hydroglyoxaline. The material is then dried 'in the usual manner and may be marketed in cakes, flakes, or any other form as may be desired. However, I may add the stabilizing agent to the oils or fats before hydrolysis, or saponification, or to the fatty acid before saponification.

The stabilizing agent aforesaid, may, how: ever be incorporated into the soap flakes, or into the solidified soap, while it is being passed through the mill, or plodder, or introduced as an added ingredient to soap solutions. or to so-called liquid soaps.

Practically any method whereby the stabilizing agent may be suitably incorporated in the final soap product will be found effective in preventing decomposition, or rancidifica tion thereof.

What I claim is: 1 I

p 1. A soap having incor orated therein,- a di-aryl tetra hydroglyoxa ine.

2. A soap having incorporated therein a tetra hydroglyoxaline derivative, wherein, aromatic radicals are substituted in the 13' positions and aliphatic radicals in one of the 2+5 positions.

3. A soap having incorporated therein a tetra hydroglyoxaline derivative, wherein,

aromatic radicals are substituted in the 1- 3.

tached thereto a radical'which is a member of the 2 modifying group, substantially as described.

6. A soap having incorporated therein a tetra hydroglyoxaline derivative, wherein, the carbon atom in the 2 position has attached thereto an aliphatic radical.

7. A soap having incorporated therein a tetra hydroglyoxaline derivative, wherein,

the carbon atom in the 2 position has attached thereto a propyl radical.

8. A soap having incorporated therein a tetra hydroglyoxaline derivative, wherein, one of the hydrogen atoms attached to the nitrogen atoms in the 1 or 3 positionsis replaced by a radical which is a member of the 13 replacement group.

9. Asoap having incorporated therein a tetra hydroglyoxahne derivative, wherein,

one of the hydrogen atoms attached to the nitrogen atoms in the 1 or 3 positions is replaced by an aliphatic radical.

, 10. A soap having incorporated therein a derivative of tetra hydroglyoxaline wherein,

. one (if the hydrogen atoms attached to the nitrogenatoms in the 1 or 3 positions is re-- placed by an aromatic radical.

11. A soap having incorporated therein a derivative oftetra hydroglyoxaline, wherein, one of the hydrogen atoms attached to the nitrogent atoms in the 1-3 positions is replaced by a phenyl radical.

12. A soap having incorporated therein a derivative of tetra hydroglyoxaline, wherein, both hydrogen atoms attached to the nitrogen 'atoms in the 1-3 positions are replaced by a radical which is a member of the 13 replacement group.

13. A soap having incorporated therein a derivative of tetra hydroglyoxaline, wherein, both hydrogen atoms attached to the nitrogen atoms in the 13 positions are replaced by' an aromatic radical. I V

' 14. A soap having incorporated therein. a derivative of tetra hydroglyoxaline, wherein, both hydrogen atoms attached to the nitrogen atoms in the 1-3 positions are replaced by a phenyl radical.

15. A soap having incorporated .therein'a derivative of tetra hydroglyoxaline, wherein, each of the carbon atoms in the 45 positions has a radical attached thereto which is a member of the 4-5 modifying group.

16. A soap having incorporated therein a derivative of tetra hydroglyoxaline, wherein, each of the carbon atoms in the 4. 5 positions has tWo radicals attached thereto both of which are members of the 4.-5 modifya, ing group) 17. A soap having incorporated therein a derivative of tetra hydroglyoxaline, wherein each of the carbon atoms in the 4-5 positions has a hydrogen atom attached thereto and substituted in one or more of'th v 123 positions by a hydrocarbon radical.

18. A soap having incorporated therein a derivative of tetra hydroglyoxaline, wherein, each ofthe carbon atoms in the 4-5 positions has two hydrogen atoms attached thereto and substituted in one or more of the 12-3 positions by a hydrocarbon radical.

19. A soap having incorporated therein a 13 diphenyl 2-propyl tetra hydroglyoxaline.

20. The method of stabilizing a soap which comprises incorporating therein a derivative of hydrogenated glyoxaline containing no strongly negative substituent groups.

21. A soap stabilized by having incorposix? "rated therein a small amount of a derivative of hydrogenated glyoxaline containing no strongly negative substituent groups.

22. A soap stabilized by having incorporated therewith from 0.10% to 1% of a derivative of hydrogenated glyoxaline containing no strongly negative substituent groups.

23. A soap having incorporated therein a derivative of dihydroglyoxaline containing no strongly negative substituent groups.

24. A soap having incorporated therein a derivative of tetrahydroglyoxaline containing no strongly negative substituent groups.

25. A soap having incorporated therein hydroglyoxalines in which the substituents in the 1345 positions are taken from the group consisting of hydrogen, hydrocarbon and furyl residues, and in the 2 position from the group consisting of hydrogen, nu hydrocarbon and furyl residues, and sul phur, and containing at least one substituent other than hydrogen.

26. A soap having incorporated therein hydroglyoxalines in which the substituents in the 13 positions are taken from the group consisting of hydrogen. hydrocarbon and furyl residues, and in the 2- position from the group consisting of hydrogen, hydrocarbon and furyl residues, and sulphur,

and containing at least one substituent other.

in the 2 position are taken from the group consisting of hydrogen, hydrocarbon and furyl residues, and sulphur, and containing at least one substituent other than hydrogen.

29..A soap having incorporated therein hydroglyoxalines in which the substituents in the l345 positions are taken from the group consisting of hydrogen and hydrocarbon residues, and in the 2 position from the group comprising hydrogen, sulphur and hydrocarbon residues, and having at least one substituent other than hydrogen.

30. 'A soap having incorporated therein hydroglyoxalines having hydrogen atoms as the 45 substituents, and as the 13 substituents a member of the group consisting of hydrogen, hydrocarbon and furyl residues, and as the 2 substituents a member of the group comprising hydrogen, sulphur, and hydrocarbon and furyl residues, and having at least one substituent other than hydrogen.

31. A soap having incorporated therewith hydroglyoxalines having hydrogen atoms as the 4-5 substituents, and as the 13 substituents members of the group consisting of hydrogen, hydrocarbon and furyl residues, and having at least one substituent other than hydrogen.

'32. A soap having incorporated therewith hydroglyoxalines having hydrogen atoms as the 4:5 substituents, and as substituents in the 2 position members of the group'consisting of hydrogen, sulphur and hydrocarbon and furyl residues.

33. The product described in claim 30 in which there are two hydrogen atoms attached to each 4-5 C atom.

34:. The product described in claim 31 in which there are two hydrogen atoms attached to each 4-5 O atom.

35. The product described in claim 32 in which there are two hydrogen atoms attached,

to each 4E5 C atom.

In testimony whereof I aflix my signature.

HAROLD A. MORTON. 

